The present invention relates to thermoplastic molding compositions and more particularly to compositions that contain any of polycarbonates, polyester carbonates and polyesters that are chain terminated with a phenolic compounds having a branched structure.
A phenolic compound having a branched structure is disclosed. The compound conforms to
HOxe2x80x94Ar1xe2x80x94Xxe2x80x94Ar2xe2x80x94[Yxe2x80x94W]nxe2x80x83xe2x80x83(1)
wherein Ar1 and Ar2 independently denote an optionally substituted mononuclear or polynuclear aromatic moiety, X and Y independently denote a single bond or a divalent radical, W denotes an optionally substituted mononuclear or polynuclear aromatic moiety or an aliphatic or cycloaliphatic radical, and
n is 1 to 5, is useful as a terminal group in polycarbonates, polyester carbonates and polyesters. Also disclosed is a process for producing such resins where the disclosed compound is a chain terminator.
Monofunctional terminal groups based on phenol, such as for example phenol, 4-alkylphenols and 4-cumylphenol, are frequently used for the production of polycarbonates (Kunststoff-Handbuch 3; L. Bottenbruch, Hanser, Mxc3xcnchen 1992, p. 127; EP-A 0 353 594).
It is not known whether these conventionally used terminal groups have a positive effect on the flow behavior and/or the zero shear viscosity and/or the thermal stability and thus whether they have a positive effect on the processing properties of the corresponding polycarbonates.
The production of polycarbonates containing branched terminal groups is in principle known and is described for example in EP-A 0 794 209 and JP-A 06 256 499.
For example p-phenylphenol is known from U.S. Pat. Nos. 3,166,606 and 3,173,891 as a chain terminator for polycarbonates. From U.S. Pat. No. 4,330,663 polyester carbonates are known in which 4-butylbenzoyl chloride is used as chain terminator.
WO-A 00/50488 describes the use of di-tert.-alkylphenol as chain terminator.
From Japanese Offenlegungsschrift 57 13 31 49 polycarbonates are known that are modified with phenylpropylphenol, alkylphenols or naphthol as terminal groups.
Tritylphenol, cumylphenol, phenoxyphenol and pentadecylphenol are described in WO-A 01/05 866 as chain terminators for polycarbonates.
From EP-A 1 048 684 and WO-A 99/36 458 polycarbonates are known that have been modified for example with 4-(1,1,3,3-tetramethylbutyl)phenol and further branched alkyl phenols.
From JP-A 06 25 64 99 polycarbonates are known containing terminal groups of the structures 
According to DE-A 38 03 939, chain terminators of the formula 
are used, wherein R1, R2, R3 are identical or different and denote C2-C12-alkyl or C8-C20-aralkyl, at least one of the radicals R1 or R2 being a C8-C20-aralkyl radical, and wherein n has a value between 0.5 and 1.
WO-A 98/22522 describes branched phenols, their use as terminal groups in polycarbonates, and polycarbonates containing such terminal groups. Furthermore, an effect of these terminal groups in the polycarbonate is said to be a lower glass transition temperature. However, no details are given either of branched phenols of the aforedescribed type or of the effect of branched terminal groups on the zero shear viscosity and thermal stability of polycarbonates.
The polyester carbonates and polyesters with known terminal groups have the disadvantage however of relatively high zero shear viscosity and/or may tend to exhibit a reduction in molecular weight and/or material discolouration under thermal stress. Thus, polycarbonates that contain secondary or tertiary hydrogen atoms, above all in the benzyl position, may be degraded under thermal stress, such as for example in an extrusion process, as a result of which the corresponding material may be discoloured. Polycarbonates that contain ester groupings as terminal groups tend under thermal stress to undergo transesterification reactions and are therefore not suitable for the melt transesterification process. (Kunststoff-Handbuch Vol. VIII, p. 150, Carl-Hanser-Verlag, Munich 1973).
Against the background of the prior art the object therefore exists of providing polycarbonates, polyester carbonates and polyestersxe2x80x94these are referred to herein below as poly(ester)(carbonate)- and/or suitable phenolic compounds as terminal groups, that do not exhibit the disadvantage of a high zero shear viscosity and at the same time do not undergo degradation under thermal stress, such as for example in an extrusion process or in injection moulding, and that may also be used in the melt transesterification process.
It has now surprisingly been found that this object is achieved by the use of terminal groups having a special branched, in particular dendrimer-like structure. These terminal groups positively influence the zero shear viscosity, i.e. the corresponding polycarbonate with a comparable molecular weight distribution exhibits a lower Zero shear viscosity and can therefore be processed more readily. In particular these special terminal groups have the advantage that they are also stable at high temperatures.
Phenolic terminal groups for polycarbonates having a dendrimer-like structure based on carbonyl-bridged or ether-bridged aryl systems have not hitherto been known.
The present invention accordingly provides polycarbonates, polyester carbonates and polyesters that contain branched, in particular dendrimer-like terminal groups based on aryl-CO- and/or aryl-O-couplings, the use of such polycarbonates, and special phenolic terminal groups suitable for use in the polycarbonates according to the invention, and/or the phenolic compounds on which the terminal groups are based.
The present invention accordingly also provides for the use of the phenolic compounds according to formula (1) for the production of terminal group-modified polymers and the phenolic compounds of the formula (2), as well as their preparation.
The phenolic compounds of the formula (1) are defined as follows:
HOxe2x80x94Ar1xe2x80x94Xxe2x80x94Ar2xe2x80x94[Yxe2x80x94W]nxe2x80x83xe2x80x83(1)
wherein Ar1 denotes an optionally substituted mononuclear or polynuclear aromatic parent group, X denotes a single bond or a divalent radical such as xe2x80x94Oxe2x80x94 or xe2x80x94COxe2x80x94,
Ar2 denotes an optionally substituted mononuclear or polynuclear aromatic parent group, Y denotes a single bond or a divalent radical such as xe2x80x94Oxe2x80x94 or xe2x80x94COxe2x80x94,
W denotes an optionally substituted mononuclear or polynuclear aromatic parent group or an aliphatic or cycloaliphatic radical, and n is a variable between 1 and 5.
Preferred are phenolic compounds of the formula (1) that correspond more specifically to the formulae (2) and (3):
Compounds of the formula (2) 
wherein
R1 denotes H, linear or branched C1-C18-alkyl, Cl or Br, preferably H or linear or branched C1-C12-alkyl, particularly preferably H or C1-C8-alkyl, and most particularly preferably H,
X denotes a single bond or a divalent radical such as xe2x80x94Oxe2x80x94 or xe2x80x94COxe2x80x94,
R2 denotes H, linear or branched C1-C18-alkyl, Cl or Br, preferably H or linear or branched C1-C12-alkyl, particularly preferably H or C1-C8-alkyl, and most particularly preferably all denote the same radical, especially H,
Y denotes a single bond or a divalent radical such as xe2x80x94Oxe2x80x94 or xe2x80x94COxe2x80x94,
R3, R7 independent from each other denote H, linear or branched C1-C18-alkyl, cyclic C5-C18-alkyl, phenyl, phenyloxy, phenylcarboxy, benzyl, benzyloxy, naphthyl, naphthyloxy or naphthylcarboxy radicals, preferably R3 equals R7 equals H, linear or branched C1-C12-alkyl, cyclic C5-C12-alkyl, phenyl, phenyloxy, benzyloxy or naphthyloxy radicals, and particularly preferably H, linear or branched C1-C12-alkyl, cyclic C5-C12-alkyl, phenyl or phenyloxy radicals, very particularly preferred R3 and R7 denote the same group or residue.
m is a number between 0 and 3, n is a number between 2 and 5, wherein m and n must total xe2x89xa65. Particularly preferred is the combination in which m=0 and n=2.
Compounds of the formula (3) 
wherein
X and Y have the meanings given above,
R4 denotes H, linear or branched C1-C18-alkyl, Cl or Br, preferably H or linear or branched C1-C12-alkyl, particularly preferably H or C1-C8-alkyl, and most particularly preferably H,
R5 denotes H, linear or branched C1-C18-alkyl, Cl or Br, preferably H or linear or branched C1-C12-alkyl, particularly preferably H or C1-C8-alkyl, and most particularly preferably all denote the same radical, in particular H,
R6 denotes linear or branched C1-C18-alkyl, cyclic C5-C18-alkyl, and preferably linear or branched C1-C12-alkyl, cyclic C5-C12-alkyl, and particularly preferably all denote the same radical, in particular linear or branched C1-C12-alkyl, as well as cyclic C5-C12-alkyl radicals, and
m is a number between 0 and 3, n is a number between 2 and 5, wherein m and n must total xe2x89xa65. Particularly preferred is the combination in which m=0 and n=2.
Most particularly preferred are in each case independently of one another the phenolic compounds that correspond to the formula 2a and 3a: 
wherein in 2a and 3a the radicals R3, R6, R7 and Y have the meanings given above.
Suitable terminal groups for the, modification of polycarbonates, polyester carbonates and polyesters are represented by formula (4):
xe2x80x83xe2x80x94Oxe2x80x94Ar1xe2x80x94Xxe2x80x94Ar2xe2x80x94[Yxe2x80x94W]nxe2x80x83xe2x80x83(4)
wherein Ar1, X, Ar2, Y and W have the meanings given above.
Particularly suitable are the terminal groups of the formulae (4a) and (4b) 
wherein the radicals X, Y, R1 to R7 and the variables n and m have the meanings given above.
Independently of one another there are most particularly preferred the terminal groups corresponding to the phenolic compounds of the formulae (2a) and (3a).
Preferred, particularly preferred, most particularly preferred or especially preferred, etc., are compounds that carry the substituents mentioned hereinbelow as preferred, particularly preferred, most particularly preferred or especially preferred, etc.
The radical definitions and explanations given above in general terms or as preferred ranges may however also be combined as desired with one another, i.e. between the respective ranges and preferred ranges. They apply as appropriate to the end products as well as to the precursors and intermediate products.
The present invention accordingly also provides thermoplastic polycarbonates, thermoplastic polyester carbonates and thermoplastic polyesters with terminal groups corresponding to the phenolic compounds of the formulae (1), (2) and (3).
Examples of phenolic compounds of the formula (1) are 3,5-diphenyloxy-4xe2x80x2-hydroxybenzophenone, 3,5-bis-(p-tert.-butylphenyloxy)-4xe2x80x2-hydroxybenzophenone, 3,5-bis-(p-n-butylphenyloxy)-4xe2x80x2-hydroxybenzophenone, 3,5-bis-(3,5-di-tert.-butylphenyl-oxy)-4xe2x80x2-hydroxybenzophenone, 3,5-bis-(p-iso-octylphenyloxy)-4xe2x80x2-hydroxybenzophenone, 3,5-dicyclooctyloxy-4xe2x80x2-hydroxybenzophenone, dicyclododecyloxy-4xe2x80x2-hydroxybenzo-phenone, 3,5-bis-(benzoyl)-4xe2x80x2-hydroxybenzophenone and 3,5-di-tert.-butyl-4xe2x80x2-hydroxy-benzophenone.
The monophenols of the formulae (2) and (3) to be used according to the invention are not known in the literature. Branched fluorine-substituted hydroxyoligo(ether ketones) are known in the literature (C. J. Hawker, F. Chu, Macromolecules 1996, 29, 4370-4380). Multiply functional hydroxy compounds such as 1,3,5-tris-(2xe2x80x2-hydroxy-benzoyl)-benzenes are also known (DE 19 59 399).
The production of the phenols of the formulae 2 and 3 may be carried out according to generally known processes. Thus, for example, phenols of the formulae 2 and 3 in which X and/or Y denote a carbonyl radical can in principle be produced by Friedel-Crafts reactions of optionally substituted aliphatic or aromatic carboxylic acid chlorides with optionally substituted aromatic compounds. Compounds of the formulae 2 and 3 in which X and/or Y denote a divalent radical such as xe2x80x94Oxe2x80x94 can in principle be produced by an Ullmann reaction of optionally substituted aromatic compounds with optionally substituted phenolates under the action of copper, at temperatures between 100xc2x0 and 230xc2x0 C. Alternatively these diaryl ethers can be produced by reacting optionally substituted arylboronic acids with phenolates. Compounds of the formulae 2 and 3 in which X and/or Y denote a single bond can be produced in a known manner by Cxe2x80x94C coupling reactions. Thus, these may be obtained for example by an Ullmann reaction of halogen-substituted aromatic compounds. Preferably iodine-substituted, optionally higher substituted aromatic compounds, are reacted under the action of copper at temperatures between 100xc2x0 and 300xc2x0 C. In order to obtain the phenols of the formulae 2 and 3 according to the invention, it is necessary in the aforementioned reactions to introduce a protected phenolic OH group into the respective compound, from which the phenolic OH group can be released, preferably in the last stage of the synthesis. Such a protected phenolic OH group may for example be introduced into the respective compound in the aforedescribed reactions by means of an optionally substituted anisole derivative. In order to release the phenolic OH group the splitting of the methyl ether may be effected for example with BBr3 in dichloromethane, with Me3SiI in chloroform, or with aqueous HBr in acetic acid.
The production of the phenols of the general formula 2a may be carried out by methods known per se in the literature (see for example C. J. Hawker, F. Chu, Macromolecules 1996, 29, 4370-4380, A. Morikawa, K. Ono, Macromolecules 1999, 32, 1062-1068). Thus, dihalobenzoic acid can be converted by means of conventional acylating reagents such as for example oxalyl chloride or thionyl chloride into the corresponding acid chloride, and then reacted with optionally substituted, but in the p-position relative to the methoxy group unsubstituted, anisole derivatives under the addition of Lewis acids. Preferably difluorobenzoic acid can be converted with oxalyl or thionyl chloride into the corresponding acid chloride. This is reacted with optionally substituted, though in the p-position relative to the methoxy group unsubstituted, anisole derivatives, preferably under the action of for example FeCl3, AlCl3, BF3, ZnCl2, SnCl4 or SbCl5, in halogenated solvents such as for example CH2Cl2 or CHCl3, at temperatures between xe2x88x9240xc2x0 C. and 80xc2x0 C. The optionally substituted dihalomethoxybenzo-phenone obtained in this way is reacted with optionally substituted phenols under the action of a base, optionally in combination with phase transfer reagents in polar aprotic solvents. Preferably the optionally substituted difluoromethoxy benzophenone is reacted with optionally substituted phenols in solvent mixtures such as: N,N-dimethylformamide/toluene, N,N-dimethylacetamide/toluene, dimethyl sulfoxide/toluene or N-methyl-pyrrolidone/toluene under the addition of for example alkali carbonates, alkali hydroxides or organic bases such as pyridine or diazabicycloundecene, optionally in combination with phase transfer reagents, at temperatures of 80xc2x0 to 200xc2x0 C. within 1 to 48 hours. Particularly preferably the optionally substituted difluoro-methoxybenzophenone is reacted with optionally substituted phenols in solvent mixtures such as N,N-dimethylacetamide/toluene, dimethyl sulfoxide/toluene or N-methylpyrrolidone/toluene under the addition of K2CO3 or K2CO3/18-crown-6, at temperatures of 100xc2x0 to 180xc2x0 C. within 3 to 24 hours. In this connection the optionally substituted difluoromethoxybenzo-phenone is stirred under reflux with optionally substituted phenols as described above for 1 to 6 hours, following which the toluene/water mixture is removed with the aid of a water separator, and the solution is then stirred for a further 1 to 16 hours at temperatures between 130xc2x0 and 180xc2x0 C. The purification of the product is carried out preferably by column chromatography on silica gel (for example silica gel 60, 0.040-0.063 mm, Merck) using a mixture of n-hexane and ethyl acetate as eluent.
As an alternative to the conditions mentioned above, the previously produced phenolate can also be reacted directly with the dihalomethoxybenzophenone. In this case the addition of toluene and the base in the process described above is omitted.
In order to release the phenolic OH group the splitting of the methyl ether may be carried out for example with BBr3 in dichloromethane, with Me3SiI in chloroform, or with aqueous HBr in acetic acid. This reaction is preferably carried out in a mixture of aqueous HBr solution and HBr solution in acetic acid.
Compounds of the formula 3a in which Y denotes for example a single bond can be produced in principle as follows: by Friedel-Crafts reaction of toluene with halogenated alkanes substituted aromatic compounds are obtained in a known manner, which are converted by subsequent oxidation of the methyl group on the aromatic compound, for example with potassium permanganate, into the correspondingly substituted benzoic acid. According to this method, 3,5-di-tert.-butylbenzoic acid for example can be produced in a known manner (see DE 32 21 818) by a Friedel-Crafts reaction of tert.-butyl chloride and toluene following by oxidation with potassium permanganate in aqueous pyridine. The substituted benzoic acid obtained in this way can be converted in a known manner with oxalyl chloride or thionyl chloride into the corresponding acid chloride. The acid chloride is reacted with optionally substituted, but in the p-position relative to the methoxy group unsubstituted, anisole derivatives, preferably under the action of for example FeCl3, AlCl3, BF3, ZnCl2, SnCl4 or SbCl5, in halogenated solvents such as for example CH2Cl2 or CHCl3, at temperatures between xe2x88x9240xc2x0 C. and 80xc2x0 C. In order to release the phenolic OH group the splitting of the methyl ether may be carried out for example with BBR3 in dichloromethane, with Me3SiI in chloroform, or with aqueous HBr in acetic acid. Preferably this reaction is carried out in a mixture of aqueous HBr solution and HBr solution in acetic acid.
Apart from the phenolic compounds of the formulae (1), (2) and (3) other phenols may also be co-used in amounts of up to 50 mole %, referred to the respective total amount of chain terminator, for the production of the polycarbonates, polyester carbonates and polyesters.
The present invention accordingly also provides for the use of the phenolic compounds of the formula (1), optionally in combination with other phenols, as chain terminators for the production of aromatic polycarbonates, aromatic polyester carbonates and aromatic polyesters, the other phenols being used in amounts of up to 50 mole %, preferably up to 25 mole %, referred to the respective total amount of chain terminators.
The present invention accordingly also provides thermoplastic polycarbonates, thermoplastic polyester carbonates and thermoplastic polyesters containing terminal groups derived from the phenolic compounds of the formulae (1), (2) and (3), illustrated by way of example but not exclusively by the polymers of the formula (5), 
wherein 
is the radical of an aromatic dicarboxylic acid, xe2x80x94Oxe2x80x94Bxe2x80x94Oxe2x80x94 is a bisphenolate radical AP@ is a whole number between 25 and 700, xe2x80x9cxxe2x80x9d and xe2x80x9cyxe2x80x9d are fractions from the range 0/p, 1/p, 2/p to p/p, where x+y=1, and xe2x80x9czxe2x80x9d=0 or 1, and at least 50 mole % of the radicals E in (5) correspond to the phenolate radicals corresponding to the phenolic compounds of the formulae (1), (2) and (3) and at most 50 mole % of the radicals E in (5) correspond to a phenolate radical other than that corresponding to the phenolic compounds of the formulae (1), (2) or (3).
According to DE-A 2 119 799 the production of polycarbonates is carried out with the participation of phenolic terminal groups according to the phase boundary process as well as the homogeneous phase process.
For the production of polycarbonates by the phase interface process, reference may be made for example to H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964, pp. 33 ff. and to Polymer Reviews, Vol. 10, xe2x80x9cCondensation Polymers by Interfacial and Solution Methodsxe2x80x9d, Paul W. Morgan, Interscience Publishers, New York 1965, Chap. VIII, p. 325.
In addition it is also possible to produce the polycarbonates according to the invention from diary carbonates and diphenols according to the known polycarbonate process in the melt, the so-called melt transesterification process, which is described for example in WO-A 01/05866 and WO-A 01/05867. Transesterification processes (acetate process and phenyl ester process) are moreover described for example in U.S. Pat. Nos. 3,494,885, 4,386,186, 4,661,580, 4,680,371 and 4,680,372, in EP-A 26 120, 26 121, 26 684, 28 030, 39 845, 91 602, 97 970, 79 075, 14 68 87, 15 61 03, 23 49 13 and 24 03 01 as well as in DE-A 14 95 626 and 22 32 977.
Diaryl carbonates within the meaning of the present invention are those carbonic acid diesters of the formula (6) 
and formula (7), 
in which R, Rxe2x80x2 and Rxe2x80x3 may independently of one another denote H, optionally branched C1-C34-alkyl,/cycloalkyl, C7-C34-alkaryl or C6-C34-aryl or C6-C34-aryloxy, for example diphenyl carbonate, butylphenyl-phenyl carbonate, di-butylphenyl carbonate, isobutylphenyl-phenyl carbonate, di-isobutylphenyl carbonate, tert.-butylphenyl-phenyl carbonate, di-tert.-butylphenyl carbonate, n-pentylphenyl-phenyl carbonate, di-(n-pentylphenyl) carbonate, n-hexylphenyl-phenyl carbonate, di-(n-hexylphenyl) carbonate, cyclohexylphenyl-phenyl carbonate, di-cyclohexylphenyl carbonate, phenylphenol-phenyl carbonate, di-phenylphenol carbonate, isooctylphenyl-phenyl carbonate, di-isooctylphenyl carbonate, n-nonylphenyl-phenyl carbonate, di-(n-nonylphenyl) carbonate, cumylphenyl-phenyl carbonate, di-cumylphenyl carbonate, naphthylphenyl-phenyl carbonate, di-naphthylphenyl carbonate, di-tert.-butylphenyl-phenyl carbonate, di-(di-tert.-butylphenyl) carbonate, dicumylphenyl-phenyl carbonate, di-(dicumylphenyl) carbonate, 4-phenoxyphenyl-phenyl carbonate, di-(4-phenoxyphenyl) carbonate, 3-pentadecylphenyl-phenyl carbonate, di-(3-pentadecylphenyl) carbonate, tritylphenyl-phenyl carbonate, di-tritylphenyl carbonate, preferably
diphenyl carbonate, tert.-butylphenyl-phenyl carbonate, di.-tert.-butylphenyl carbonate, phenylphenol-phenyl carbonate, di-phenylphenol carbonate, cumylphenyl-phenyl carbonate, di-cumylphenyl carbonate, particularly preferably diphenyl carbonate.
Diphenols for the polycarbonates according to the invention may for example be hydroquinone, resorcinol, dihydroxybiphenyls, bis-(hydroxyphenyl)-alkanes, bis-(hydroxyphenyl)-cycloalkanes, bis-(hydroxyphenyl)-sulfides, bis-(hydroxyphenyl)ethers, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulfones, bis-(hydroxy-phenyl)-sulfoxides, xcex1,xcex1xe2x80x2-bis-(hydroxyphenyl)-diisopropylbenzenes, as well as their nuclear-alkylated and nuclear-halogenated compounds, and also xcex1,xcfx89-bis-(hydroxyphenyl)-polysiloxanes.
Preferred diphenols are for example 4,4xe2x80x2-dihydroxybiphenyl (DOD), 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC), 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-1-phenylethane, 1,1-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 1,3-bis-[2-7(4-hydroxyphenyl)-2-propyl]-benzene (bisphenol M), 2,2-bis-(3-methyl-4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 2,2bis-(3, 5-dimethyl-4-hydroxyphenyl)-sulfone, 2.4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane and 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.
Particularly preferred diphenols are for example 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]-benzene (bisphenol M), 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 1,1-bis-(4-hydroxyphenyl)-1-phenyl-ethane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane,
0.2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane and 1, 1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC).
Most particularly preferred are 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol M) and 1,1-bis-(4-hydroxy-phenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC).
The diphenols may be used alone or as a mixture with one another; homopolycarbonates as well as copolycarbonates are suitable. The diphenols are known in the literature or can be produced by processes known in the literature (see for example H. J. Buysch et al., Ullmann""s Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5th Ed., Vol. 19, p. 348).
There may also be used minor amounts, preferably amounts between 0.05 and 2.0 mole % referred to the moles of diphenols employed, of trifunctional or multifunctional compounds, in particular those with three or more than three phenolic hydroxy groups, as so-called branching agents. Deviations from the idealised formula (5), which is shown only by way of example, thereby obviously occur since branching structures are involved, in contrast to the specified structures D and B.
Some of the compounds that can be used containing three or more than three phenolic hydroxy groups are for example phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane, tri-(4-hydroxyphenyl)-phenylmethane, 2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane, 2,4-bis-(4-hydroxyphenylisopropyl)-phenol, 2.6-bis-(2-hydroxy-5xe2x80x2-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(3,4-dihydroxyphenyl)-propane, hexa-[4-(4-hydroxyphenyliso-propyl)-phenyl]-orthoterephthalic acid ester, tetra-[4-(4-hydroxyphenylisopropyl)-phenoxy]-methane, tetra-(4-hydroxyphenyl)-methane and 1,4-bis-(4xe2x80x2,4xe2x80x3-dihydroxy-triphenyl)-methylbenzene.
Further possible branching agents are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and
3,3-bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.
The branching agents which are optionally co-used in an amount of 0.05 to 2 mole % referred to diphenols employed, may either be added together with the diphenols themselves and the molecular weight regulators according to the invention to the aqueous alkaline phase, or are added, dissolved in an organic solvent, before the phosgenation.
The aromatic polycarbonates of the present invention have weight average molecular weights MW (determined by gel permeation chromatography and calibration with a polystyrene standard) between 5000 and 200000, preferably between 10000 and 80000 and particularly preferably between 15000 and 40000.
The relative solution viscosities are correspondingly between 1.10 and 1.60 measured in methylene chloride (0.5 g of polycarbonate in 100 ml of methylene chloride at 23xc2x0 C.).
Polyester carbonates according to the invention are those that are built up from at least one diphenol, from at least one aromatic dicarboxylic acid and from carbonic acid.
Suitable aromatic dicarboxylic acids are for-example orthophthalic acid, terephthalate acid, isophthalic acid, tert.-butylisophthalic acid, 3,3xe2x80x2-diphenyldicarboxylic acid, 4,4xe2x80x2-diphenyletherdicarboxylic acid, 4,4xe2x80x2-diphenylsulfonedicarboxylic acid, 3,4xe2x80x2-benzo-phenonedicarboxylic acid, 2,2-bis-(4-carboxyphenyl)-propane and trimethyl-3-phenyl-indane-4,5-dicarboxylic acid.
Of the aromatic dicarboxylic acids, terephthalic acid and/or isophthalic acid are particularly preferably used.
Suitable diphenols are those mentioned hereinbefore for the polycarbonate production. Carbonic acid may be incorporated either via phosgene or via diphenyl carbonate into the polyester carbonates, depending on the choice of production process, i.e. depending on whether phase interface polycondensation or melt transesterification is employed for the polyester carbonate production.
The same applies as regards the aromatic dicarboxylic acids; these are employed either as aromatic dicarboxylic acid dichlorides in the two-phase interface process or as dicarboxylic acid diesters in the melt transesterification process.
The production of the polyester carbonates according to the invention is carried out according to know production methods, i.e. as already mentioned, according to the phase interface process or according to the melt transesterification process for example.
The polyester polycarbonates according to the invention may be linear as well as branched in a known manner. The aromatic polyester carbonates of the present invention have mean weight-average molecular weights MW (determined by gel permeation chromatography with polystyrene calibration) preferably between 10000 and 250000.
The molar ratio of carbonate units to aromatic dicarboxylate units in the polyester carbonates according to the invention is preferably 95:5 to 5:95, more preferably between 90:10 to 10:90, particularly preferably between 80:20 and 20:80, and most particularly preferably between 60:40 and 40:60.
In the case of the polyesters (5) according to the invention xe2x80x9czxe2x80x9d may be 0 as well as 1.
Aromatic polyesters according to the invention are those formed from at least one diphenol and at least one aromatic dicarboxylic acid.
Suitable diphenols and dicarboxylic acids are those mentioned hereinbefore for the polyester carbonate production.
The aromatic polyesters according to the invention are produced by known production processes (see for example Kunststoff-Handbuch, Vol. VIII, p. 695 ff, Carl-Hanser-Verlag Munich, 1973).
The aromatic polyesters according to the invention may be linear as well as branched in a known manner.
The aromatic polyesters according to the invention have mean weight-average molecular weights MW (determined by the light scattering method) preferably between 25000 and 70000; this corresponds to degrees of polymerisation Ap@ in formula (5) of about 80 to 270, where xe2x80x9cxxe2x80x9d=1, xe2x80x9cyxe2x80x9d=0 and xe2x80x9czxe2x80x9d=1.
The amount of monophenols of the formulae (1), (2) or (3) according to the invention that are to be used for the production of the polycarbonates, polyester carbonates or polyesters according to the invention is between 0.5 mole % and 8 mole %, preferably between 2 mole % and 6 mole % referred to the diphenols used in each case.
Further suitable chain terminators are the customary monophenols, such as for example phenol, 4-alkylphenols and 4-cumylphenol.
The present invention accordingly also provides a process for the production of the polycarbonates, polyester carbonates or polyesters according to the invention from diphenols, monophenols, carbonic acid derivatives and/or dicarboxylic acid derivatives according to process conditions known per se, which process is characterised in that monophenols of the formulae (1), (2) or (3) are employed as chain terminators in amounts of 0.5 mole % to 8 mole %, preferably 2 mole % to 6 mole %, referred in each case to moles of diphenols, in which connection up to 50 mole %, preferably up to 25 mole %, referred in each case to the total amount of chain terminators, may be replaced by other monophenols.
In the case of the phase interface polycondensation process the chain terminators of the formulae (1), (2) or (3) may be added before, during or after the phosgenation in solution. The solvents suitable for dissolving the chain terminators of formulae (1), (2) or (3) are for example methylene chloride, chlorobenzene or acetonitrile, as well as mixtures of these solvents.
In the case of the melt transesterification process, in accordance with the process according to the invention it is possible to add the chain terminators of the formulae (1), (2) or (3) at any point in the reaction; in this connection the addition may be split into several portions.
The present invention also provides the polycarbonates, polyester carbonates and polyesters obtainable by the process according to the invention.
Diphenols for the production of the polycarbonates, polyester carbonates and polyesters according to the invention may also be polymers or condensates containing phenolic terminal groups, with the result that polycarbonates or polyester carbonates or polyesters with block structures may also be incorporated according to the invention.
The polycarbonates, polyester carbonates and polyesters according to the invention may be worked up in a known manner and processed into suitable moulded articles, for example by extrusion or injection moulding. Other aromatic polycarbonates and/or other aromatic polyester carbonates and/or other aromatic polyesters may also be mixed in a known manner with the polycarbonates, polyester carbonates and polyesters according to the invention.
There may also be added in the usual amounts to the polycarbonates, polyester carbonates and polyesters according to the invention additives that are conventionally used for these thermoplastics, such as fillers, UV stabilisers, thermal stabiliser, antistatics and pigments; the mould release behavior, the flow behavior and/or the flame resistance may also be improved if necessary by adding external mold release agents, flow improvers and/or flameproofing agents (for example alkyl and aryl phosphites, phosphates, phosphanes, low molecular weight carboxylic acid esters, halogenated compounds, salts, chalk, quartz flour, glass and carbon fibres, pigments and combinations thereof. Such compounds are described for example in WO 99/55772, pp. 15-25, and in xe2x80x9cPlastics Additivesxe2x80x9d, R. Gxc3xa4chter and H. Mxc3xcller, Hanser Publishers 1983.
The polycarbonates, polyester carbonates and polyesters according to the invention, optionally mixed with other thermoplastics and/or conventional additives, may be processed into suitable molded articles/extrudates, and used in all cases where known polycarbonates, polyester carbonates and polyesters are already employed. On account of their property profile they are suitable in particular as substrate materials for optical data storage media such as for example CD, CD-R, DVD or DVD-R, but may also be used for example as films in the electrical sector, as molded parts in vehicle production, and as sheets for coverings in the safety sector.
Further possible applications of the polycarbonates according to the invention include:
1. Safety panels, which as is known are required in many areas of housings, vehicles and aircraft, as well as helmet shields.
2. Production of foils, especially ski foils.
3. Production of molded articles (see for example U.S. Pat. No. 2,964,794), for example 1- to 5-gallon water containers.
4. Production of light-permeable panels, in particular hollow-cavity panels, for example for covering buildings such as railways, greenhouses and lighting installations.
5. Production of optical data storage media.
6. Production of traffic light housings or vehicle number plates.
7. Production of foams (see for example DE-AS 1 031 507).
8. Production of fibres and threads (see for example DE-AS 1 137 167 and DE-OS 1 785 137).
9. As translucent plastics materials with a glass fibre content for light technology purposes (see for example DE-OS 1 554 020).
10. As translucent plastics materials containing barium sulfate, titanium dioxide and/or zirconium oxide and/or organic polymeric acrylate rubbers (EP-A 634 445, EP-A 269324) for the production of light-permeable and light-scattering molded parts.
11. Production of precision injection-molded small parts, such as for example lens mountings. For this purpose polycarbonates are used that contain glass fibres, which optionally may additionally contain about 1-10 wt. % of MOS2, referred to the total weight.
12. Production of optical instrument parts, in particular lenses for photographic cameras and film cameras (see for example DE-OS 2 701 173).
13. As light-transmission carriers, in particular as light-conducting cables (see for example EP-A1 0 089 801).
14. As electrical insulation materials for electrical leads and for plug housings as well as plug-and-socket connectors.
15. Production of mobile telephone housings having improved resistance to perfume, shaving water and sweat.
16. Network interface devices.
17. As carrier material for organic photoconductors.
18. Production of lamps/lights, e.g. headlamps, scattered light panels or internal lenses.
19. For medical applications, e.g. oxygenators, dialysis equipment.
20. For foodstuff applications, e.g. bottles, utensils and chocolate molds.
21. For applications in the automobile sector where contact with fuels and lubricants may occur, such as for example bumpers, optionally in the form of suitable blends with ABS or suitable rubbers.
22. For sports articles, such as for example slalom poles or ski shoe fastenings.
23. For household articles, for example kitchen sink units and letter box housings.
24. For housings, for example electrical distribution cabinets.
25. Housings for electric toothbrushes and hairdryers.
26. Transparent washing machine Abullseyes@ with improved resistance to detergents.
27. Protective goggles optical correction glasses.
28. Lamp coverings for kitchen appliances with improved resistance to kitchen atmospheres, in particular oil vapours.
29. Packaging films for medicaments.
30. Chip boxes and chip carriers.
31. For other applications, such as for example stall-feeding doors or animal cages.
The molded articles and extrudates produced from the polymers according to the invention are also covered by this application.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.